Phenylaminoalkylated cellulosic textiles and process of chemically modifying them



United States Patent PHENYLAMINOALKYLATED CELLULOSIC TEX- TILES AND PROCESS OF CHEMICALLY MODI- FYING THEM Wilson A. Reeves and John D. Guthrie, New Orleans,

La., assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Application April 10, 1953, Serial No. 348,138

11 Claims. (Cl. 817) (Granted under Title 35, U. S. Code (1952), see. 266) A non-exclusive, irrevocable, royalty-free license in the invention herein described, for all governmental purposes, throughout the world, with the power to grant sublicenses for such purposes, .is hereby granted to the Government of the United States of America.

This invention relates to chemically modified cellulosic textiles such as slivers, yarns, threads, and fabrics.

More particularly, in one important aspect, the invention provides a process by which aromatic radicals containing primary amino groups on the ring can be chemically bonded to molecules of a cellulosic textile, without materially altering the physical properties of the textile.

Primary amino groups attached to an aromatic ring are capable of entering into diazo reactions to form a wide variety of colored compounds. For over years various attempts to attach such aminoaryl groups to the molecules of cellulosic textiles have been reported. The previously reported processes involve drastic reaction conditions, such as autoclaving, or prolonged refluxing of the textiles in contact with reagents capable of swelling cellulosic materials. Such drastic reaction conditions materially alter the physical properties of cellulosic textiles.

As herein employed, the term aminoalkylated cellulosic textile refers to a cellulosic textile in which alcoholic hydrogen atoms have been replaced by aminoalkyl radicals. Such textiles are characterized by a marked affinity for acid dyestuffs and other valuable properties. Various processes of preparing aminoalkylated cellulosic textiles are known. U. S. 2,459,222 describes a particularly suitable process of preparing such textiles by reacting a cellulosic textile with Z-aminoethyl sulfuric acid in the presence of aqueous alkali. Aminoalkylated cellulosic textiles produced by reacting cellulosic textiles with 3-aminopropyl sulfuric acid by a similar procedure have analogous properties. The aminoalkylated cellulosic textiles can be employed in the present process .in the form of slivers, yarns, threads, or fabric.

In one aspect, the process of the present invention comprises producing nitroaryl-substituted aminoalkylated cellulosic textiles by reacting a halogen and nitro-substituted aromatic hydrocarbon, which is capable of reacting with a primary alkyl amine in the presence of alkali, with an aminoalkylated cellulosic textile in the presence of dilute aqueous alkali, using reaction conditions under which the reactants are substantially inert to the cellulosic textile from which the aminoalkylated cellulosic textile was produced. The reaction produces cellulosic textiles in which alcoholic hydrogen atoms have been replaced by N-(nitroaryl)aminoalkyl radicals. Primary amino groups of the aminoalkylated cellulosic textile are converted to secondary amino groups which are attached to an aromatic radical in addition to an aliphatic radical. For example, a cellulosic textile in which alcoholic hydrogen atoms are replaced by 2-aminoethyl radicals can be converted to a textile in which alcoholic hydrogen atoms are replaced by a N-(2,4-dinitrophenyl)-2-aminoethyl radical.

2,750,249 Patented June 12, 1956 The novel nitroaryl-substituted aminoalkylated cellulosic textiles provided by this invention retain the aflinity for acid dyestuffs which is characteristic of aminoalkylated cellulosic textiles. The nitroaryl-substituted textiles are useful for the purposes for which aminoalkylated textiles are used and, in addition, are valuable intermediates for the production of further modified textiles.

In another aspect, the process of the present invention comprises producing aminoaryl-substituted aminoalkylated cellulosic textiles by reacting a nitroaryl-substituted aminoalkylated cellulosic textile with a nitro group reducing agent dissolved in an aqueous solution.

The novel aminoaryl-substituted aminoalkylated cellulosic textiles provided by this invention are cellulosic textiles in which alcoholic hydrogen atoms have been replaced by N-(aminoaryl)aminoalkyl radicals. These textiles retain the afiinity for acid dyes which is characteristic of aminoalkylated cellulosic textiles. The aminoaryl-substituted aminoalkylated cellulosic textiles are useful for the purposes for which aminoalkylated cellulosic textiles are used and, in addition, are valuable intermediates for the production of further modified cellulosic textiles, including colored cellulosic textiles containing diazo groups attached to the molecules of the textile.

In another aspect, the process of the present invention comprises, producing colored diazoaryl-substittued aminoalkylated cellulosic textiles by diazotizing primary arylamino groups of aminoaryl-substituted aminoalkylated cellulosic textiles and coupling the diazotized groups with a. phenolic compound.

The diazotization and coupling procedures produce colored cellulosic textiles in which alcoholic hydrogen atoms have been replaced by alkyl radicals substituted with amino groups which are attached to an aromatic radical containing diazo groups which are attached to phenolic compounds. Such textiles are characterized by a uniformity of color throughout each fiber. They exhibit a marked resistance to changes in color due to ordinary laundering. Such textiles exhibit physical properties substantially comparable to the cellulosic textiles from which they were produced.

Aminoalkylated cotton threads and fabrics produced by the process of U. S. 2,459,222 comprise preferred starting materials for use in the present process. As shown by the patent, these materials have residual free hydroxyl groups. Where the threads or fabrics are aminoalkylated by an analogous process in which the Z-aminoethyl sulfuric acid is replaced by an acid sulfuric acid ester of an aminoalkanol of from about 2 to 4 carbon atoms, especially 3-aminopropanol, the products are particularly suitable because of their close resemblance to the untreated cellulosic textiles in hand and feel.

Halogen and nitro-substituted aromatic hydrocarbons which are capable of reacting with a primary alkyl amine in the presence of alkali comprise a rather well defined class of organic compounds characterized by the presence of a plurality of nitro groups at least one of which is in an ortho or para position relationship with a halogen atom. The capability of a given compound to so react can, of course, be readily determined by observing whether it reacts with a simple alkyl amine in the presence of alkali. A preferred class of such compounds comprises chloro and pitro-substituted benzene hydrocarbons in which at least one nitro group is in an ortho or para position relationship with a chlorine atom. Such compounds include 1-chloro-2,4,6-trinitrobenzene and l-chloro-2,4-dinitrobenzene. The latter is preferred.

The conditions under which the aminoalkylated cellulosic textile is reacted with the substituted aromatic hydrocarbon in the presence of the dilute aqueous alkali can be varied widely. The textile can be contacted with the reactants, in any order, at temperatures ranging from about 25 C. to 100 C. using conditions Qf temperature, pressure and concentration under which the reactants are substantially inert to the cellulosic textile from which the aminoalkylate'd cellulosic textile was produced. Whether a given set Ofreaction conditions meets this requirement can readily be determined by subjecting a sample of the cellulosic textile to the reaction conditions. The reaction is preferably conducted by immersing the textile in a heterogeneous aqueous medium containing from about 0.5 to 10.0% alkali metal hydroxide and from about 1.0 to 10.0% of the substituted aromatic hydrocarbon maintained at a temperature of from about 50 to 100 C. until the desired degree of reaction occurs. The extent of the change in the physical properties of the textile tends to increase as the reaction time increases.

The nitro groups of the nitroaryl-substituted aminoalkylated cellulosic textiles can be reduced by the conventional nitro group reducingprocedures involving aqueous reaction mediums. The nitro groups are preferably reduced in a dilute aqueous solution of a water soluble hydr-osulfite maintained at from about 25 C. to 100 C. until the desired degree of reduction is obtained. The use of sodium hydrosulfite is preferred.

The aminoaryl-substituted aminoalkylated cellulosic textiles can be diazotized and coupled by the conventional diazotization and coupling procedures employing temperatures below about 15 C. The diazotized amino groups can be coupled with aromatic amines and phenols such as the resorcinols, the naphthols, aniline, the toluidines, and their homologs and analogs.

The following examples are illustrative of the invention:

Example 1 Nizroaryl-substitutin.-The aminoalkylated cellulosic textile used was an 80 x 80 cotton print cloth containing 0.67% nitrogen in the form of 2-aminoethyl groups produced by the process of Patent No. 2,459,222.

Portions of the aminoalkylated cloth were immersed for about minutes in a heterogeneous aqueous medium containing from 1 to 2% sodium hydroxide and from 1 to 2% 1-chloro-2,4-dinitrobenzene maintained at from 70 to 90 C.

Portions of the aminoalkylated cloth were similarly treated with 1-chloro-2,4,6-trinitro-benzene.

Portions of the cloth from which the aminoalkylated cloth was produced were similarly treated with both 1- chloro 2,4 dinitrobenzene and 1-chloro-2,4,6-trinitrobenzene.

A comparison of the amount of nitrogen introduced by the treatments is reported in the following table. The cloth from which the aminoalkylated cloth was produced underwent substantially no reaction. The dinitro-substituted hydrocarbon reacted more uniformly than the trinitrosubstituted hydrocarbon. Both the 2,4-dinitro-, and the 2,4,6-trinitrophenyl-substituted Z-arninoethylated cotton cloths had physical properties and an affinity for acid dyes comparable to the aminoalkylated cloth from which they were produced.

Example 2 Nitro group reducti0n.-The nitro groups of the textiles produced in Example 1 were reduced by agitating the 4 fabric in a warm aqueous solution of sodium hydrosulfite (NazS204).

The 2,4-diaminophenyl-substituted and the 2,4,6-t1'iaminophenyl-substituted 2-aminoethylated cotton cloths so produced exhibited physical properties comparable to the physical properties of the aminoalkylated cloth from which they were produced.

Example 3 Diazotization.Portions of the 2,4-diaminophenyl-substituted aminoalkylated fabric produced in Example 2 were agitated in cool dilute solutions of nitrous "acid and hydrochloric acid. 10 to 15 minutes agitation at from about 5 to 10 C. in water solutions containing from about 5 to 20% nitrous acid and about 2 to 10% hydrochloric acid (by wt.) produced substantially complete diazotization.

Example 4 C0upling.Portions of the fabric diazotized in Example 3 were transferred from the diazotization reaction mixture to coupling baths comprising dilute aqueous solutions containing a .soluble carbonate and a phenolic compound. The use of coupling baths containing about 10% sodium carbonate and from about 1 to 2% of the phenolic compound at temperatures of from about 10 to 15 C. produced substantially complete coupling.

A portion of the fabric coupled in this manner With 1- naphthol-S-sulfonic acid had a dark red-brown color.

A portion of fabric coupled in this manner with 8- arnino l-naphthol-3,6-disulfonic acid had a dark purple color.

We claim:

1. A process comprising: immersing a Z-aminoethylated cotton fabric for from about 3 to 60 minutes in an aqueous medium containing from about 1.0 to 10.0% alkali metal hydroxide and from about 1.0 to 10.0% l-chloro- 2,4-dinitrobenzene maintained at from about 25 C. to C. and continuing the treatment until primary amino groups of the aminoethylated cellulosic material have been converted to secondary amino groups attached to a 2,4-dinitrophenyl radical in addition to the ethyl radical.

2. The process comprising reacting amino lower-alkylated cellulosic textiles, having residual free hydroxyl groups in the cellulose molecule, with a 'halogenand nitro-substituted benzene hydrocarbon containing at least one nitro radical in a position from the group consisting of ortho and para with relation to the halogen atom, in the presence of dilute aqueous alkali, at a temperature from about 25 C. to about 100 C. thereby maintaining the reactants inert to said residual free hydroxyl groups, and continuing the reaction until primary amino groups of the amino lower-alkylated cellulosic material have been converted to secondary amino groups attached to a nitrophenyl radical produced by removing the halogen atom from the halogenand nitro-substituted benzene hydrocarbon in addition to the lower alkyl radical of the amino lower-alkylated cellulosic textile.

3. The process comprising reacting amino lower-alkylated cellulosic textiles, having residual free hydroxyl groups in the cellulose molecule, with a halogenand nitro-substituted benzene hydrocarbon containing at least one nitro radical in a position from the group consisting of ortho and para with relation to the halogen atom, in the presence of dilute aqueous alkali, at a temperature from about 25 C. to about 100 C. thereby maintaining the reactants inert to said residual free hydroxyl groups, continuing the reaction until primary amino groups of the amino lower-alkylated cellulosic material have been converted to secondary amino groups attached to a nitrophenyl radical produced by removing the halogen atom from the halogenand nitro-substituted benzene hydrocarbon in addition to the lower alkyl radical of the amino loWer-alkylated cellulosic textile, and reducing the nitro groups of the nitrophenyl-substituted amino lower alkylated cellulosic textile to amino groups.

4. A process of coloring an amino lower-alkylated cellulosic textile, having residual free hydroxyl groups in the cellulose molecule, which comprises reacting said amino lower-alkylated cellulosic textile with a halogenand nitro-substituted benzene hydrocarbon containing at least one nitro radical in a position from the group consisting of ortho and para with relation to the halogen atom, in the presence of dilute aqueous alkali, at a temperature from about 25 C. to about 100 C. thereby maintaining the reactants inert to said residual free hydroxyl groups, continuing the reaction until primary amino groups of the amino lower-alkylated cellulosic material have been converted to secondary amino groups attached to a nitrophenyl radical produced by removing the halogen atom from the halogenand nitro-substituted benzene hydrocarbon in addition to the lower alkyl radical of the amino lower-alkylated cellulosic textile, reducing the nitro groups of the nitrophenyl-substituted amino loweralkylated cellulosic textile to amino groups, diazotizing the reduced nitro groups, and coupling the diazo groups with a phenolic compound.

5. Phenylamino lower-alkylated cellulosic textile having physical properties not materially different from amino lower-alkylated cellulosic textiles in which the ether groups attached to the cellulose molecules consist essentially of N-(substituted-phenyl)amino lower-alkylated radicals in which the substituted-phenyl radical is a phenyl radical in which hydrogen atoms have been replaced by at least one radical of the group consisting of nitro, amino, and diazo radicals.

6. Phenylamino lower-alkylated cellulosic textiles having physical properties not materially difierent from amino lower-alkylated cellulosic textiles in which the ether groups attached to the cellulose molecules consist essentially of N-(nitrophenyl)amino lower-alkyl radicals.

7. Phenylamino lower-alkylated cellulosic textiles having physical properties not materially difierent from amino lower-alkylated cellulosic textiles in which the ether groups attached to the cellulose molecules consist essentially of N-(aminophenyl)amino lower-alkyl radicals.

8. Phenylamino lower-alkylated cellulosic textiles having physical properties not materially different from amino lower-alkylated cellulosic textiles in which the ether groups attached to the cellulose molecules consist essentially of N-(diazophenyl)amino lower-alkyl radicals.

9. Phenylaminoethylated cotton textiles having physical properties not materally difierent from aminoethylated cotton textiles in which the ether groups attached to the cellulose molecules consist essentially of N-(2,4-dinitrophenyl)-2-aminoethyl radicals.

10. Phenylaminoethylated cotton textiles having physical properties not materially different from aminoethylated cotton textiles in which the ether groups attached to the cellulose molecules consist essentially of N-(2,4- diaminophenyl)-2-aminoethyl radicals.

l1. Phenylarninoethylated cotton textiles having physical properties not materially different from aminoethylated cotton textiles in which the ether groups attached to the cellulose molecules consist essentially of N-(2,4,6- trinitrophenyl)-2-aminoethyl radicals.

References Cited in the file of this patent UNITED STATES PATENTS 2,459,222 Guthrie Jan. 18, 1949 FOREIGN PATENTS 346,385 Great Britain Mar. 30, 1931 347,117 Great Britain Apr. 21, 1931 347,263 Great Britain Apr. 23, 1931 

4. A PROCESS OF COLORING AN AMINO LOWER-ALKYLATED CELLULOSIC TEXTILE, HAVING RESIDUAL FREE HYDROXYL GROUPS IN THE CELLULOSE MOLECULE, WHICH COMPRISES REACTING SAID AMINO LOWER-ALKYLATED CELLULOSIC TEXTILE WITH A HALOGEN AND NITRO-SUBSTITUTED BENZENE HYDROCARBON CONTAINING AT LEAST ONE NITRO RADICAL IN A POSITION FROM THE GROUP CONSISTING OF ORTHO AND PARA WITH RELATION TO THE HALOGEN ATOM, IN THE PRESENCE OF DILUTE AQUEOUS ALKALI, AT A TEMPERATURE FROM ABOUT 25* C. TO ABOUT 100* C. THEREBY MAINTAINING THE REACTANTS INERT TO SAID RESIDUAL FREE HYDROXYL GROUPS, CONTINUING THE REACTION UNTIL PRIMARY AMINO GROUPS OF THE AMINO LOWER-ALKYLATED CELLULOSIC MATERIAL HAVE BEEN CONVERTED TO SECONDARY AMINO GROUPS ATTACHED TO A NITROPHENYL RADICAL PRODUCED BY REMOVING THE HALOGEN ATOM FROM THE HALOGEN- AND NITRO-SUBSTITUTED BENZENE HYDROCARBON IN ADDITION TO THE LOWER ALKYL RADICAL OF THE AMINO LOWER-ALKYLATED CELLULOSIC TEXTILE, REDUCING THE NITRO GROUPS OF THE NITROPENYL-SUBSTITUTED AMINO LOWERALKYLATED CELLULOSIC TEXTILE TO AMINO GROUPS, DIAZOTIZING ARE REDUCED NITRO GROUPS, AND COUPLING THE DIAZO GROUPS WITH A PHENOLIC COMPOUND.
 5. PHENYLAMINO LOWER-ALKYLATED CELLULOSIC TEXTILE HAVING PHYSICAL PROPERTIES NOT MATERIALLY DIFFERENT FROM AMINO LOWER-ALKYLATED CELLULOSIC TEXTILES IN WHICH THE ETHER GROUPS ATTACHED TO THE CELLULOSE MOLECULES CONSIST ESSENTIALLY OF N-(SUBSTITUTED-PHENYL) AMINO LOWER-ALKYLATED RADICALS IN WHICH THE SUBSTITUTED-PHENYL RADICAL IS A PHENYL RADICAL IN WHICH HYDROGEN ATOMS HAVE BEEN REPLACED BY AT LEAST ONE RADICAL OF THE GROUP CONSISTING OF NITRO, AMINO, AND DIAZO RADICALS. 